Microwave dielectric ceramic composition

ABSTRACT

A dielectric ceramic composition wherein the dielectric constant ∈ is large, the temperature coefficient τf of the resonance frequency is close to 0, and which as a large Q value, is obtained by adding to and blending with a ceramic composition whose τf of the resonance frequency is large on the plus side a ceramic composition whose temperature coefficient τf is large on the minus side. In an Li 2 O—R 2 O 3 —TiO 2 -based composition, an improved dielectric constant ∈ can be achieved by introducing a specific quantity of Bi 2 O 3 , and τf can be shifted to the plus side and in addition a considerable improvement in Qf achieved by introducing a specific quantity of MO, where M is one or two of Ca and Sr. Furthermore, by introducing a specific quantity of Na 2 O together with the MO (where M is one or two of CA and Sr), in particular in the case of material of ∈r&gt;150, it is possible to control τf to the vicinity of 0 while maintaining Qf at an high value.

TECHNICAL FIELD

The present invention relates to a microwave dielectric ceramic composition employed in resonator materials or capacitor materials etc used in the microwave region of a few GHz.

BACKGROUND ART

Dielectrics are used in the resonators, filters, or capacitors that are used in transceivers for for example satellite communication broadcasting or mobile identification devices using microwaves of a few GHz.

As such dielectric ceramic materials, for example BaO—TiO₂—Nd₂O₃—Bi₂O₃ compositions have been proposed (Laid-open Japanese Patent Application No. Sho. 61-8806). The dielectric constant ∈ of this composition is of the order or 70 to 110; when dielectric resonators or capacitors are constructed, materials of larger dielectric constant ∈ are preferred since the larger the dielectric constant ∈ of the material that is used, the smaller are the dimensions of the resonator.

Conventional materials of large dielectric constant ∈ include for example SrTiO₃ and CaTiO₃ etc; while their dielectric constant ∈ is very large at 300 and 180, the temperature coefficient τf of the resonance frequency is extremely large at +1700 ppm/°C. and +800 ppm/°C., which means that it is not possible to use them.

Accordingly, as a method of lowering the temperature coefficient τf of a dielectric ceramic composition, the method is available of preparing a material whose dielectric constant ∈ is as large as possible and whose temperature coefficient τf has a negative value; with this method, a ceramic composition can be obtained by a suitable composition whose dielectric constant ∈ is large and whose temperature coefficient τf of resonance frequency is small.

For example, Laid-open Japanese Patent Publication No. H. 5-211009 proposes the obtaining of a ceramic composition of large dielectric constant ∈ and whose temperature coefficient of resonance frequency τf is close to zero, by preparing a material represented by the compositional formula (A¹⁺ _(1/2).B³⁺ _(1/2)) TiO₃ where A¹⁺ is Li¹⁺, and B³⁺ is Nd³⁺, Sm³⁺, Co³⁺ or Pr³⁺, constituting a material of large dielectric constant ∈ and wherein the temperature coefficient τf has a negative value.

However, the demands for miniaturization of portable electronic terminal equipment have today become so exacting that a material having even higher dielectric constant ∈ is earnestly sought for the dielectric material of resonators, filters and capacitors employed in such devices.

DISCLOSURE OF THE INVENTION

In view of the characteristics required for a dielectric ceramic composition for microwaves, an object of the present invention is to obtain a dielectric ceramic composition wherein the dielectric constant ∈ is large, the temperature coefficient τf of the resonance frequency is close to 0, and which has a large Q value, by adding to and blending with a ceramic composition whose τf of the resonance frequency is large on the plus side to a ceramic composition whose temperature coefficient τf is large on the minus side.

With the object of providing a dielectric ceramic composition whose dielectric constant ∈ is large, whose temperature coefficient of resonance frequency τf is close to 0, and whose Q value is large, the present inventors have previously proposed a dielectric ceramic composition represented by the compositional formula Li₂O—Na₂O—Bi₂O₃—R₂O₃—TiO₂, where R₂O₃ is one or two or more of La₂O₃, Nd₂O₃, Sm₂O₃, Co₂O₃ or Pr₂O₃ (Japanese Patent Application Number 2000-337141).

Also, the present inventors have proposed (Japanese Patent Application Number 2000-340104) a dielectric ceramic composition represented by the compositional formula Li₂O—Bi₂O₃—R₂O₃—SrTiO₃, where R₂O₃ is one or two or more of La₂O₃, Nd₂O₃, Sm₂O₃, Co₂O₃ or Pr₂O₃.

As a result of further assiduous investigation, the present inventors discovered that an excellent dielectric characteristic could be obtained in stable fashion by co-presence of specific quantities of Bi₂O₃, Na₂O and MO (where M is one or two of Ca and Sr) in the one or two or more of La, Nd, Pr and Sm constituting R, in the Li₂O—R₂O₃—TiO₂-based composition.

Specifically, the present inventors discovered that, in an Li₂O—R₂O₃—TiO₂-based composition, an improved dielectric constant ∈ could be achieved by introducing a specific quantity of Bi₂O₃, and τf could be shifted to the plus side and in addition the effect of a considerable improvement in Qf achieved by introducing a specific quantity of MO (where M is one or two of Ca and Sr).

They discovered that, by introducing MO, τf becomes too large, making it difficult to make τf approach 0 while maintaining Qf at a fixed value, so, by introducing a specific quantity of Na₂O together with the MO (where M is one or two of Ca and Sr), in particular in the case of material of ∈r>150, it was possible to control τf to the vicinity of 0 while maintaining Qf at an high value, and thereby perfected the present invention.

Specifically, the present invention consists in a microwave dielectric ceramic composition represented by the compositional formula

aLi₂O-bNa₂O-cR₂O₃-dBi₂O₃-eMO-fTiO₂

(where a+b+c+d+e+f=100, a, b, c, d, e and f being mol %) where R includes one or two or more of Nd, Sm, Pr, and La, M includes one or two of Ca and Sr and a, b, c, d, e, f satisfy 5<a<15, 0<b<10, 3<c<15, 1<d<15, 1<e<30, and 40<f<75.

BEST MODE FOR CARRYING OUT THE INVENTION

In the present invention, in the Li₂O—Na₂O—R₂O₃—Bi₂O₃—MO—TiO₂-based composition (where R is one or two or more of Nd, Sm, Pr, and La and M is one or two of Ca and Sr), if Li₂O is less than 5 mol %, the dielectric constant is low and τf becomes too large on the plus side; while if it exceeds 15 mol %, Li₂O being of low melting-point, this is undesirable because there is the problem that the ceramic composition reacts and fuses with the base plate or base powder during sintering. A range of 5<a<15 mol % is therefore specified for Li₂O (a).

Also, if Na₂O exceeds 10 mol %, this is undesirable because it gives rise to the problem that τf becomes too large on the plus side, and Qf falls. Accordingly, a range of 0<b<10 mol % is specified for Na₂O (b).

If R₂O₃ (R³⁺ is one or two or more of Nd³⁺, Sm³⁺, Pr³⁺, and La³⁺) is less than 3 mol %, the dielectric constant is low and Q is also poor; if it exceeds 15 mol %, there is little benefit and costs are increased, which is undesirable. A range of 3<c<15 mol % is therefore specified for R₂O₃ (c).

Bi₂O₃ has the effect of increasing the dielectric constant ∈ and a content thereof of at least 1 mol % is necessary; however, because of its lower melting-point, if it exceeds 15 mol %, there is a risk that the ceramic composition will react and fuse with the base plate or base powder on sintering; this is therefore undesirable. Accordingly, a range of 1<d<15 mol % is specified for Bi₂O₃ (d).

Also, the content of MO (where M is one or two of Ca and Sr) has the benefit of improving Qf and improving the temperature coefficient τf; however, if it is less than 1 mol %, there is little benefit in terms of improving Qf and improving the temperature coefficient τf and if it exceeds 30 mol %, the temperature coefficient τf becomes too large on the plus side, which is undesirable. Accordingly, a range of 1<e<30 mol % is specified for MO (e).

In addition, if TiO₂ is less than 40 mol %, the required crystalline phase is not obtained and the required dielectric characteristic is not obtained; if it is more than 75 mol %, the problem arises that a phase consisting of TiO₂ on its own appears, severely lowering Qf, which is undesirable. A range of 40<f<75 mol % is therefore specified for TiO₂ (f).

EXAMPLE

High-purity TiO₂, Bi₂O₃, Li₂CO₃, Nd₂O₃, Sm₂O₃, Pr₆O₁₁, La₂O₃, Na₂CO₃, CaCO₃, and SrCO₃ were weighed out and blended such that the required mol percentages were obtained in the raw material, as in Table 1 to Table 2, so as to obtain a mixture of compositional formula aLi₂O-bNa₂O-cR₂O₃-dBi₂O₃-eMO-fTiO₂ (where a+b+c+d+e+f=100, a, b, c, d, e and f being mol %, R includes one or two or more of Nd, Sm, Pr, and La, M includes one or two of Ca and Sr); mixing was performed for 5 to 20 hours using a ball mill.

After mixing, calcining was performed for one hour to five hours at 700° C. to 1000° C. After this, the mixture was again pulverized for 2 to 50 hours, and the pulverized powder was mixed with organic binder and pelletized, then sieved and molded into the shape of a disc of diameter 10 mm, thickness 6 mm with a pressure of 2 to 3 T/cm². This molding was then sintered for one to five hours at 1200° C. to 1400° C., and both faces thereof polished so that the thickness of the sintered body was half its diameter, thereby producing a measurement sample.

The dielectric constant ∈, Q value and temperature coefficient τf of resonance frequency of the measurement samples obtained were measured at a measurement frequency of 3 GHz, using the method of Hakki and Coleman. The measurement results for the dielectric characteristic of the measurement samples are shown in Table 3.

TABLE 1 Li₂O Na₂O R₂O₃(R = Na,Sm,Pr,La) (a) (b) (c) 1 9.50 3.97 Sm³⁺ 8.77 2 10.58 4.31 9.03 3 10.00 5.02 9.57 4 9.70 5.56 9.98 5 10.50 0.38 Nd³⁺ 7.97 6 10.75 0.69 8.24 7 9.80 0.93 8.44 8 10.70 1.24 8.72 9 8.00 4.01 Pr³⁺ 0.5 + Nd³⁺ 0.5 5.86 10 9.40 4.35 6.06 11 7.00 5.03 6.45 12 8.00 5.38 6.65 13 9.00 0.30 Pr³⁺ 6.60 14 9.00 0.60 6.86 15 7.00 0.90 7.11 16 7.00 1.20 7.37 17 8.00 4.14 La³⁺ 0.5 + Nd³⁺ 0.5 6.85 18 9.00 4.49 7.05 19 9.50 5.19 7.47 20 7.00 5.56 7.68 1 10.50 0 Nd³⁺ 7.64 2 9.00 0 Pr³⁺ 6.35 3 8.82 0 La³⁺ 4.41 4 9.50 4.14 Sm³⁺ 13.69 5 10.50 0.30 Nd³⁺ 10.98 6 9.00 0.30 Pr³⁺ 9.17 7 8.00 8.33 Pr³⁺ 0.5 + Nd³⁺ 0.5 8.33 8 9.00 6.67 Pr³⁺ 12.00 9 8.00 6.67 La³⁺ 0.5 + Nd³⁺ 0.5 8.33

TABLE 2 Bi₂O₃ MO TiO₂ (d) CaO(e) SrO(e) (f) 1 4.72 0.00 9.52 63.52 2 4.86 0.00 8.31 62.90 3 5.15 0.00 5.83 64.43 4 5.38 0.00 3.92 65.46 5 3.10 16.79 0.00 61.26 6 3.20 15.67 0.00 61.44 7 3.28 14.81 0.00 62.73 8 3.39 13.66 0.00 62.28 9 5.86 14.81 0.00 61.44 10 6.06 13.66 0.00 60.48 11 6.45 11.32 0.00 63.75 12 6.65 10.13 0.00 63.20 13 2.57 22.49 0.00 59.05 14 2.67 21.43 0.00 59.45 15 2.77 20.36 0.00 61.86 16 2.87 19.28 0.00 62.28 17 6.85 8.92 0.00 65.25 18 7.05 7.69 0.00 64.72 19 7.47 5.19 0.00 65.18 20 7.68 3.92 0.00 68.16 1 2.97 18.18 0.00 60.71 2 2.47 23.53 0.00 58.85 3 4.41 23.53 0.00 58.82 4 0 0.00 8.92 63.75 5 0 17.07 0.00 61.15 6 0 22.49 0.00 58.05 7 8.33 0.00 0.00 67.00 8 4.67 0.00 0.00 67.67 9 8.33 0.00 0.00 68.67

TABLE 3 Dielectric characteristic εr Qf(GHz) τf(ppm/° C.) 1 131 3202 17 2 133 3134 8 3 135 3198 −2 4 137 3157 −6 5 151 2132 10 6 153 2107 3 7 155 2064 −5 8 157 1987 −12 9 167 1767 22 10 170 1723 14 11 173 1702 0 12 175 1678 −8 13 179 1545 14 14 182 1512 2 15 185 1448 −4 16 188 1398 18 17 198 1312 23 18 202 1280 10 19 208 1223 1 20 217 1187 −5 1 151 2209 41 2 180 1533 86 3 205 1109 143 4 111 3256 35 5 129 2389 68 6 142 1644 123 7 165 978 4 8 177 745 −5 9 195 465 2

INDUSTRIAL APPLICABILITY

In an Li₂O—R₂O₃—TiO₂-based composition, an improved dielectric constant ∈ can be achieved by introducing a specific quantity of Bi₂O₃, and τf can be shifted to the plus side and in addition the effect of a considerable improvement in Qf achieved by introducing a specific quantity of MO (where M is one or two of Ca and Sr). Furthermore, by introducing a specific quantity of Na₂O together with the MO (where M is one or two of Ca and Sr), in particular in the case of material of ∈r>150, it is possible to control τf to the vicinity of 0 while maintaining Qf at an high value.

A dielectric ceramic composition according to the present invention is ideal for the dielectric material of resonators, filters and capacitors used in transceivers for satellite communication broadcasting or mobile identification devices etc that make use of microwaves of a few GHz, since, as is clear from the Practical Examples, its dielectric constant ∈ is large, its temperature coefficient τf of resonance frequency approaches 0, and a large Q value is obtained therewith. 

What is claimed is:
 1. A microwave dielectric ceramic composition represented by the compositional formula aLi₂O-bNa₂O-cR₂O₃-dBi₂O₃-eMO-fTiO₂ wherein a+b+c+d+e+f=100, a, b, c, d, e and f being mol %, wherein R is selected from the group consisting of Nd, Sm, Pr, and La, M is selected from the group consisting of Ca and Sr, and a, b, c, d, e and f satisfy: 5<a<15, 0<b<10, 3<c<15, 1<d<15, 1<e<30, 40<f<75.
 2. A microwave dielectric ceramic composition according to claim 1, wherein b is at least 0.3. 